Electrolyte for non-aqueous cell and non-aqueous secondary cell

ABSTRACT

In a rechargeable non-aqueous electrolyte secondary battery using positive electrodes, negative electrodes and a non-aqueous electrolytic solution, additives to the electrolytic solution are used in combination, preferably in combination of at least two compounds selected from o-terphenyl, triphenylene, cyclohexylbenzene and biphenyl, and thus there are provided batteries excellent in safety and storage characteristics.

This is a divisional application of application number 10/333,617 filedJan. 22, 2003, which is a national phase under 35 USC 371 ofPCT/JP2001/007434 filed Aug. 29, 2001, which is based on Japaneseapplication number 2000-311626 filed Oct. 12, 2000, the entire contentsof each of which are incorporated by reference herein.

TECHNICAL FIELD

The present invention relates to a non-aqueous electrolytic solutionwhich can ensure safety of batteries at the time of overcharging withimproving recovery characteristics of the batteries after storage athigh temperatures, and to a non-aqueous type secondary battery usingsaid electrolytic solution.

BACKGROUND ART

Recently, AV devices and electronic devices such as personal computersof portable or cordless type have been rapidly developed, and secondarybatteries which are small in size, light in weight and high in energydensity are earnestly demanded as electric sources for driving thesedevices. Among them, non-aqueous electrolytic solution secondarybatteries using a negative electrode containing lithium as an activematerial are hopefully expected as batteries having high voltage andhigh energy density.

In the above batteries, lithium-containing metal oxides which show avoltage on the order of 4 V are used for positive electrode activematerials, and materials capable of intercalation or deintercalation oflithium, such as carbonaceous materials, are used for negativeelectrodes.

One of the most important tasks in these non-aqueous electrolyticsolution batteries is to ensure the safety.

Particularly, in lithium ion secondary batteries, when they are chargedin excess of a given charging voltage due to, for example, troubles ofcharging control circuits, they are in overcharged state, and lithiumions in the positive electrode are excessively extracted and migrate tonegative electrode to cause absorption of lithium in an amount largerthan the prescribed design capacity in the negative electrode or tocause precipitation of lithium as metallic lithium on the surface ofnegative electrode. If the batteries in such a state are furtherforcedly charged, internal resistance of the batteries increases andgeneration of heat due to the Joule's heat becomes great to causeabnormal heat generation, and, in the worst case, to result in thermalrunaway. By providing a current interrupting switch of temperaturesensing type (for example, a positive temperature coefficient thermistor(PTC) or a temperature fuse) outside the batteries, the current isinterrupted without fail, and safety can be ensured at the time ofgeneration of abnormal heat. Furthermore, in order to solve the problemof overcharge, a means of interrupting the charging current upon sensingthe change of internal pressure of batteries is generally employed asdisclosed in U.S. Pat. No. 4,943,497.

However, in the case of using such a mechanical current interruptingmechanism, reduction of cost is difficult and, furthermore, with thebatteries becoming smaller and thinner, it becomes structurallydifficult to insert the mechanism in the batteries.

For solving the above problems, there is proposed a method of adding tothe electrolytic solution an additive which causes a reversible redoxreaction, thereby to self-consume the electric energy introduced intothe batteries as a redox shuttle (for example, JP-A-1-206571,JP-A-6-338347, JP-A-7-302614, etc.).

However, in the method of using the redox shuttle, when the overchargingcurrent becomes great, there are limits in charge transfer reaction rateand lithium ion transfer rate, and, thus, it cannot be said that themethod provides a sufficient safety.

For solving the above problems, JP-9-50822, JP-A-10-50342, JP-9-106835,JP-10-321258, Japanese Patent No. 2939469, and JP-A-2000-58117 propose ameans of adding to batteries an aromatic compound having a methoxy groupand a halogen group, biphenyl or thiophene, or an aromatic ethercompound, which polymerizes at the time of overcharging to result inrising of temperature and, thus, to ensure the safety.

DISCLOSURE OF INVENTION

In the case of the batteries in which a current interrupting switch oftemperature sensing type (for example, a positive temperaturecoefficient thermistor (PTC) or a temperature fuse) is provided outsidethe batteries against abnormal heat generation, when an excessivelylarge overcharging current (5-6 C) of more than 5-6 times the ratedcapacity passes, the device per se generates heat due to the current andresistance increases, thereby interrupting the current, and thus thesafety can be ensured, but in the case of a current generally used forcharging and discharging the batteries (less than 1-2 C at the maximum),the rising of temperature is insufficient and the resistance does notincrease. When overcharging is carried out at such a current value, thesafety cannot be sufficiently ensured. If the setting is made so thatthe resistance increases in the generally used current region, naturallythe inherent performance of the batteries are damaged.

In the case of adding to the batteries the above-mentioned additivessuch as aromatic compound having a methoxy group and a halogen group,biphenyl or thiophene, and an aromatic ether compound, it has beenconfirmed that in the generally used current ranges, the additivespolymerize on the electrodes in overcharged state, and the safety isimproved.

However, it has been found that these additives must be added in anamount of not less than 1% by weight for ensuring the safety at the timeof overcharging, but if the additives are added in a large amount, in anshelf life test, for example, an environment test (80° C.) whichsupposes the case of leaving them in a car in summer, these additivespartially react to cover the active material, resulting in considerabledeterioration of the battery characteristics.

The above phenomenon is considered to occur because oxidativepolymerization potential of the additives lowers due to exposure of thebattery to a high temperature environment, and, furthermore, thepotential distribution in the charged electrode is not uniform andhigher potential portions are partially present, and, as a result, theadditives react even in the ordinary environment of potential at whichbattery is used.

The above problem of deterioration due to storage can be solved, forexample, by using an additive high in oxidative polymerization startingpotential (for example, cyclohexylbenzene), but in this case, since thereaction potential of the additive is rather high at the time of theovercharging, the safety of overcharging cannot sufficiently be ensured.

The present invention solves the above problems and to provide a batteryexcellent in high-temperature storage characteristics while ensuring thesafety at overcharging.

In order to solve the above problems, according to the presentinvention, in a non-aqueous electrolytic solution in which anelectrolyte is dissolved in a non-aqueous solvent, two or more organiccompounds differing in oxidative polymerization reaction potential areadded. Preferably, organic compounds of relatively low oxidationreaction potential are added in a very small amount, preferably not lessthan 0.01% by weight and less than 1.0% by weight based on the totalamount of the electrolytic solution, thereby to control the recoverycharacteristics after storage and the safety during overcharging.Specifically, it is preferred to add at least two organic compoundsselected from o-terphenyl, triphenylene, cyclohexylbenzene and biphenyl.

It is preferred that not less than 1.0% by weight and not more than 3.0%by weight of o-terphenyl and not Tess than 0.01% by weight and less than1.0% by weight of triphenylene are contained in the non-aqueous solvent.

Furthermore, it is preferred that not less than 1.0% by weight and notmore than 5.0% by weight of cyclohexylbenzene and not less than 0.01% byweight and less than 1.0% by weight of biphenyl are contained in thenon-aqueous solvent.

Moreover, it is preferred that not less than 1.0% by weight and not morethan 5.0% by weight of cyclohexylbenzene and not less than 0.01% byweight and less than 1.0% by weight of o-terphenyl are contained in thenon-aqueous solvent.

Further, it is preferred that not less than 1.0% by weight and not morethan 5.0% by weight of cyclohexylbenzene, not less than 0.01% by weightand less than 1.0% by weight of o-terphenyl and not less than 0.01% byweight and less than 1.0% by weight of biphenyl are contained in thenon-aqueous solvent.

Furthermore, it is preferred that all of o-terphenyl, triphenylene,cyclohexylbenzene and biphenyl are contained in the non-aqueous solventand the total amount of them is 0.4-5% by weight based on thenon-aqueous solvent.

These organic compounds are particularly effective when the positiveelectrodes comprise a material containing a lithium-containing metaloxide and the negative electrodes comprise a material containinggraphite, and the non-aqueous electrolytic solution exerts the highereffect when it is an electrolytic solution in which a lithium salt as asolute is dissolved in a non-aqueous solvent mainly composed of a cycliccarbonate and a chain carbonate. The cyclic carbonate is preferably atleast one compound selected from ethylene carbonate (EC), propylenecarbonate (PC), butylene carbonate (BC) and vinylene carbonate (VC).

The chain carbonate is preferably at least one compound selected fromdimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate(EMC), methylpropyl carbonate (MPC) and ethylpropyl carbonate (EPC).

BRIEF DESCRIPTION OF DRAWING

FIG. 1 is a longitudinal sectional view of a cylindrical battery in theexamples of the present invention and in the comparative examples.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, recovery characteristics after storage andsafety during overcharging can be controlled by adding two or moreorganic compounds differing in oxidative polymerization reactionpotential to the electrolytic solution.

Examples of organic compounds differing in oxidative polymerizationpotential contained in the electrolytic solution for non-aqueous typebatteries in which an electrolyte is dissolved in a non-aqueous solventare o-terphenyl, triphenylene, cyclohexylbenzene and biphenyl. As to thecontent of the organic compounds, the weight of the organic compound ofrelatively higher oxidative polymerization potential is preferably notless than 1.0% by weight and not more than 5.0% by weight based on thetotal amount of the non-aqueous electrolytic solution. The weight of theorganic compound of relatively lower oxidative polymerization potentialis preferably not less than 0.01% by weight and less than 1.0% by weightbased on the total amount of the non-aqueous electrolytic solution.Furthermore, the weight ratio of the organic compound of relativelyhigher oxidative polymerization reaction potential and the organiccompound of relatively lower oxidative polymerization reaction potentialis preferably not lower than 20:1 and not higher than 2:1, morepreferably not lower than 10:1 and not higher than 4:1.

In order to improve the recovery characteristics after storage, theamount of the organic compound of relatively lower oxidativepolymerization starting potential (for example, biphenyl) is preferablysmaller, but in order to ensure the safety at overcharging, the organiccompound must react as much as possible at overcharging, namely, theamount is preferably rather larger.

According to the present invention, two or more organic compoundsdiffering in oxidative polymerization reaction potential (hereinaftersometimes referred to as “additives”) are used, and the amount of theorganic compound of relatively lower oxidative polymerization startingpotential (for example, biphenyl) is conspicuously reduced in thissystem, thereby maintaining excellent storage characteristics, and onthe other hand the organic compounds react only slightly at theovercharging, whereby polarization at the overcharging increases, andthe organic compound of relatively higher oxidative polymerizationstarting potential (for example, cyclohexylbenzene) react at an earlystage, and thus the safety can be ensured. As a result, there can beattained both the recovery properties after storage and the insurance ofsafety at overcharging, which cannot be attained with addition of eachorganic compound singly.

Since the additives in the present invention do not aim at an action asredox shuttles, the oxidation reaction is desirably irreversible andthey differ in purpose from JP-A-7-302614 and JP-A-9-50822 which aim atreversibility of redox reaction.

As the lithium-containing composite oxides used as positive electrodeactive materials in the present invention, mention may be made of, forexample, Li_(x)CoO_(z), Li_(x)NiO_(Z) (U.S. Pat. No. 4,302,518),Li_(x)MnO_(Z), Li_(x)Co_(y)Ni_(1-y)O_(Z) (JP-A-63-299056),Li_(x)Co_(f)V_(1-f)O_(Z), Li_(x)Ni_(1-y)M_(y)O_(Z) (M=Ti, V, Mn, Fe),Li_(x)Co_(a)Ni_(b)M_(c)O_(Z) (M=Ti, Mn, Al, Mg, Fe, Zr), Li_(x)Mn₂O₄,Li_(x)Mn_(2(1-y))M_(2y)O₄ (M=Na, Mg, Sc, Y, Fe, Co, Ni, Ti, Zr, Cu, Zn,Al, Pb, Sb) (x=0-1.2, y=0-1.0, f=0.9-0.98, z=1.9-2.3, a+b+c=1.0, 0□a□1,0□b□1, 0□c<1). The value x is a value before starting of charging anddischarging, which increases or decreases by charging and discharging.

The lithium-containing composite oxides used as positive electrodeactive materials in the present invention can be prepared by mixingcarbonate, nitrate, oxide or hydroxide of lithium with carbonate,nitrate, oxide or hydroxide of a transition metal such as cobalt,manganese or nickel at a desired composition, grinding the mixture andfiring the powder or by a solution reaction. The firing method isespecially preferred, and the firing temperature can be 250-1500° C. atwhich a part of the mixed compound is decomposed and molten. The firingtime is preferably 1-80 hours. The firing gas atmosphere can be any ofair atmosphere, oxidizing atmosphere or reducing atmosphere, and has nospecial limitation.

In the present invention, a plurality of different positive electrodeactive materials may be used in combination.

As current collectors of positive electrodes, there may be used anyelectron conductors as long as they do not undergo chemical changes inthe constructed batteries. For examples, as materials of the currentcollectors, there may be used stainless steel, aluminum, titanium andcarbon, and aluminum or aluminum alloys are especially preferred. As forthe shape of the current collectors, they may be in the form of foil,film, sheet, net, punched material, lath, porous material, foamedmaterial, fiber group, shaped nonwoven fabric, and the like. The surfaceof the current collectors may be made rough by a surface treatment.Thickness thereof is not particularly limited, and those of 1-500 μm areused.

The negative electrode materials used in the present invention may belithium alloys, alloys, intermetallic compounds, carbons, organiccompounds, inorganic compounds, metal complexes and organic highmolecular compounds, which are capable of absorbing and releasinglithium ions. These may be used each alone or in combination.

As the carbonaceous materials, mention may be made of for example,cokes, pyrolytic carbons, natural graphite, artificial graphite,mesocarbon microbeads, graphitized mesophase spherules, vapor depositedcarbons, glassy carbons, carbon fibers (polyacrylonitrile fibers, pitchfibers, cellulose fibers and vapor deposited carbon fibers), amorphouscarbons, and carbons prepared by firing organic materials. These may beused each alone or in combination. Among them, preferred are graphitematerials such as those obtained by graphitizing mesophase spherules,natural graphite and artificial graphite. These negative electrodematerials may be used as composites, and, for example, combinations ofcarbon with alloys, carbon with inorganic compounds, and the like can beconsidered.

In the present invention, since Li is contained in the positiveelectrode active material, negative electrode materials which do notcontain Li (such as carbon) can be used. Moreover, when Li is added tosuch negative electrode materials which do not contain Li in a smallamount (about 0.01-10 parts by weight based on 100 parts by weight ofthe negative electrode materials), even if the materials become inactiveowing to the reaction of a part of Li with electrolyte, Li can besupplemented with Li contained in the negative electrode materials,which is preferred. Li can be contained in the negative electrodematerials, for example, in the following manner. That is, lithium metalwhich is molten by heating is coated on a current collector to which anegative electrode material is pressed, thereby impregnating thenegative electrode material with Li, or lithium metal is previouslyapplied to electrode group by press bonding and Li is electrochemicallydoped in the negative electrode material in the electrolytic solution.

As current collectors of negative electrodes, there may be used anyelectron conductors as long as they do not undergo chemical changes inthe constructed batteries, For example, as materials of the collectors,there may be used stainless steel, nickel, copper, titanium, etc. Copperor copper alloys are especially preferred.

As for the shape of the current collectors, they may be in the form offoil, film, sheet, net, punched material, lath, porous material, foamedmaterial, fiber group, shaped nonwoven fabric, and the like. Moreover,the surface of the current collectors may be made rough by a surfacetreatment. Thickness is not particularly limited, and those of 1-500 μmare used.

The non-aqueous electrolytic solution in the present invention comprisesa solvent and a lithium salt dissolved in the solvent, As thenon-aqueous solvents, mention may be made of cyclic carbonates such asethylene carbonate (EC), propylene carbonate (PC), butylene carbonate(BC) and vinylene carbonate (VC), non-cyclic carbonates such as dimethylcarbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC),ethylpropyl carbonate (EPC), methylpropyl carbonate (MPC),methylisopropyl carbonate (MIPC) and dipropyl carbonate (DPC), aliphaticcarboxylic acid esters such as methyl formate, methyl acetate, methylpropionate and ethyl propionate, γ-lactones such as γ-butyrolactone,non-cyclic ethers such as 1,2-dimethoxyethane (DME), 1,2-diethoxyethane(DEE) and ethoxymethoxyethane (EME), cyclic ethers such astetrahydrofuran and 2-methyltetrahydrofuran, dimethyl sulfoxide,1,3-dioxolan, alkyl phosphate esters such as trimethyl phosphate,triethyl phosphate and trioctyl phosphate, and fluorides of them. Thesemay be used each alone or in admixture of two or more. Among them, it ispreferred to use a mixed system of a cyclic carbonate and a non-cycliccarbonate or a mixed system of a cyclic carbonate, non-cyclic carbonateand an aliphatic carboxylic acid ester as a main component.

The lithium salts which are dissolved in these solvents include, forexample, LiClO₄, LiBF₄, LiPF₆, LiAlCl₄, LiSbF₆, LiSCN, LiCl, LiCF₃SO₃,LiCF₃CO₂, LiAsF₆, LiN(CF₃SO₂)₂, Li₂B₁₀Cl₁₀ (JP-A-57-74974),LiN(C₂F₅SO₂)₂, LiPF₃(CF₃)₃, LiPF₃(C₂F₅)₃, etc. These may be containedeach alone or in combination of two or more in the electrolyticsolution, etc. Among them, it is especially preferred that the solutioncontains LiPF₆.

Especially preferable non-aqueous electrolytic solution in the presentinvention is one which contains at least ethylene carbonate andethylmethyl carbonate and LiPF₆ as a lithium salt. The amount of theelectrolytic solution contained in the battery is not particularlylimited, and it can be used in a necessary amount depending on theamount of positive electrode active material and that of negativeelectrode material and the size of the battery. The amount of thelithium salt dissolved in the non-aqueous solvent is not particularlylimited, but is preferably 0.2-2 mol/l, especially preferably 0.5-1.5mol/l.

The electrolytic solution is ordinarily used by impregnating or fillinga separator such as of porous polymer or nonwoven fabric with theelectrolytic solution.

Moreover, there may be used a gelled electrolyte comprising an organicsolid electrolyte containing the non-aqueous electrolytic solution. Asthe organic solid electrolyte, polymeric matrix materials such aspolyethylene oxide, polypropylene oxide, polyvinylidene fluoride andderivatives, mixtures and composites of these materials are effective.Especially preferred are copolymers of vinylidene fluoride andhexafluoropropylene and mixtures of polyvinylidene fluoride andpolyethylene oxide.

As the separator, an insulating microporous thin film having a high ionpermeability and a desired mechanical strength is used. The separatorpreferably has a function of closing the pores at a temperature of 80°C. or higher to enhance the resistance. Sheets or nonwoven fabrics madefrom olefin polymers comprising one or combination of polypropylene andpolyethylene or glass fibers are used from the points of organic solventresistance and hydrophobic properties. Pore diameter of the separator ispreferably in such a range that active materials, binders and conductingagents which are released from the electrode sheets do not permeatethrough the pores, and, for example, the pore diameter is preferably0.01-1 μm. The thickness of the separator is generally 5-300 μm. Theporosity is determined depending on the permeability to electron or ion,kind of materials or film thickness, and is desirably 30-80%.

The shape of batteries can be any of sheet type, cylinder type, flattype, rectangular type, etc. When the shape of batteries is sheet type,cylinder type or rectangular type, the mix of positive electrode activematerial or negative electrode material is used mainly by coating on acurrent collector, then drying and compressing the collector.

The shape of the rolled electrodes in the present invention is notnecessarily in the form of true cylinder, and may be in the form ofellipsoidal cylinder having a ellipsoidal section or in the form ofsquare pillar such as rectangle.

Preferred combinations in the present invention are combinations of thepreferred chemical materials and the preferred battery constitutingparts mentioned above. Especially preferred are those which containLi_(x)CoO₂, Li_(x)NiO₂, Li_(x)Mn₂O₄ (0□x□1) as positive electrode activematerials, and acetylene black as a conducting agent. The currentcollector of positive electrode is made of stainless steel or aluminum,and is in the form of net, sheet, foil or lath. The negative electrodematerial preferably contains at least one compound such as alloy andcarbonaceous material. The current collector of negative electrode ismade of stainless steel or copper and is in the form of net, sheet, foilor lath. Carbon materials such as acetylene black and graphite as theelectron conducting agent may be contained in the mix used together withpositive electrode active materials or negative electrode materials. Asthe binders, there may be used fluorine-containing thermoplasticcompounds such as polyvinylidene fluoride and polytetrafluoroethylene,polymers containing acrylic acid, and elastomers such asstyrene-butadiene rubber and ethylene-propylene terpolymer each alone orin admixture. The electrolytic solution preferably contains cyclic ornon-cyclic carbonates such as ethylene carbonate, diethyl carbonate,dimethyl carbonate and ethylmethyl carbonate or additionally aliphaticcarboxylic acid esters such as methyl acetate and methyl propionate, andLiPF₆ as a lithium salt. The separator preferably comprisespolypropylene or polyethylene each alone or in combination. The batterymay have any shapes such as cylindrical shape, flat shape, andrectangular shape. The battery preferably has a means for ensuringsafety against errors in working (e.g., an internal pressure releasingtype safety valve, a separator which enhances resistance at hightemperatures).

EXAMPLES

Examples of the present invention will be explained below referring tothe drawing.

Example 1

FIG. 1 is a longitudinal sectional view of the cylindrical battery usedin this example. In FIG. 1, the reference numeral 1 indicates a batterycase made by working a stainless steel plate having resistance toorganic electrolytic solution, 2 indicates a sealing plate provided witha safety valve, 3 indicates an insulation packing, 4 indicates anelectrode plate group, and positive electrode and negative electrodewith separator interposed between the positive electrode and thenegative electrode are rolled a plurality of times into a spiral formand inserted in the case 1. A positive electrode lead 5 is drawn fromthe positive electrode and connected to the sealing plate 2, and anegative electrode lead 6 is drawn from the negative electrode andconnected to the bottom of the battery case 1. The reference numeral 7indicates an insulation ring, which is provided at the upper and lowerportions of the electrode plate group 4. The positive electrode, thenegative electrode, and others will be explained in detail below.

The positive electrode was made in the following manner. Li₂CO₃ andCo₃O₄ were mixed and fired at 900° C. for 10 hours to prepare an LiCoO₂powder, This powder was mixed with 3% of acetylene black and 7% of afluorocarbon polymer binder based on the weight of the LiCoO₂ powder,followed by suspending the mixture in an aqueous carboxymethyl cellulosesolution to prepare a positive electrode mix paste. The resultingpositive electrode mix paste was coated on the surface of an aluminumfoil of 20 um in thickness which was a positive electrode currentcollector, and the coat was dried, followed by rolling to make apositive electrode plate of 0.18 mm in thickness, 37 mm in width and 390mm in length.

For the negative electrode, a mesophase spherule which was graphitizedat a high temperature of 2800° C. (hereinafter referred to as “mesophasegraphite”) was used. This mesophase graphite was mixed with 3% of astyrene-butadiene rubber based on the weight of the mesophase graphite,and then the mixture was suspended in an aqueous carboxymethyl cellulosesolution to prepare a paste. This negative electrode mix paste wascoated on both sides of a Cu foil of 0.02 mm in thickness and dried,followed by rolling to make a negative electrode plate of 0.20 mm inthickness, 39 mm in width and 420 mm in length.

A lead made of aluminum was attached to the positive electrode plate anda lead made of nickel was attached to the negative electrode plate, andthe positive electrode plate and the negative electrode plate with apolyethylene separator of 0.018 mm in thickness, 45 mm in width and 840mm in length interposed between the positive electrode plate and thenegative electrode plate were rolled into a spiral form and inserted ina battery case of 17.0 mm in diameter and 50.0 mm in height. Theelectrolytic solution used was prepared by dissolving 1 mol/liter ofLiPF6 in a mixed solvent comprising EC and EMC at a volume ratio of30:70, and as additives, 2% by weight of o-terphenyl and 0.2% by weightof triphenylene based on the total amount of the electrolytic solutionwere added to the electrolytic solution. The electrolytic solution waspoured into the battery case, and then the case was sealed to make abattery 1 (battery capacity: 800 mAh) of the present invention.

Example 2

A cylindrical battery of spiral type was made in the same manner as inExample 1, except that cyclohexylbenzene in an amount of 2% by weightand biphenyl in an amount of 0.2% by weight based on the total amount ofthe electrolytic solution were used as the additives to the electrolyticsolution. The thus obtained battery was referred to as battery 2 of thepresent invention.

Example 3

A cylindrical battery of spiral type was made in the same manner as inExample 1, except that cyclohexylbenzene in an amount of 2% by weightand o-terphenyl in an amount of 0.2% by weight based on the total amountof the electrolytic solution were used as the additives to theelectrolytic solution. The thus obtained battery was referred to asbattery 3 of the present invention.

Example 4

A cylindrical battery of spiral type was made in the same manner as inExample 1, except that cyclohexylbenzene in an amount of 2% by weight,biphenyl in an amount of 0.2% by weight and o-terphenyl in an amount of0.2% by weight based on the total amount of the electrolytic solutionwere used as the additives to the electrolytic solution. The thusobtained battery was referred to as battery 4 of the present invention.

Example 5

A cylindrical battery of spiral type was made in the same manner as inExample 1, except that cyclohexylbenzene in an amount of 2% by weight,biphenyl in an amount of 0.2% by weight, o-terphenyl in an amount of0.2% by weight and triphenylene in an amount of 0.1% by weight based onthe total amount of the electrolytic solution were used as the additivesto the electrolytic solution. The thus obtained battery was referred toas battery 5 of the present invention.

Comparative Example 1

A cylindrical battery was made in the same manner as in Example 1,except that the additives to the electrolytic solution were not used.The thus obtained battery was referred to as a comparative battery(battery 6).

Comparative Example 2

A cylindrical battery of spiral type was made in the same manner as inExample 1, except that biphenyl was used in an amount of 2.0% by weightbased on the total amount of the electrolytic solution as the additiveto the electrolytic solution. The thus obtained battery was referred toas a comparative battery (battery 7).

Comparative Example 3

A cylindrical battery of spiral type was made in the same manner as inExample 1, except that cyclohexylbenzene was used in an amount of 2.0%by weight based on the total amount of the electrolytic solution as theadditive to the electrolytic solution. The thus obtained battery wasreferred to as a comparative battery (battery 8).

Comparative Example 4

A cylindrical battery of spiral type was made in the same manner as inExample 1, except that o-terphenyl was used in an amount of 2.0% byweight based on the total amount of the electrolytic solution as theadditive to the electrolytic solution. The thus obtained battery wasreferred to as a comparative battery (battery 9).

Comparative Example 5

A cylindrical battery of spiral type was made in the same manner as inExample 1, except that biphenyl was used in an amount of 0.2% by weightbased on the total amount of the electrolytic solution as the additiveto the electrolytic solution. The thus obtained battery was referred toas a comparative battery (battery 10).

Then, as overcharging tests, 20 cells each of the batteries 1-5 of thepresent invention and the comparative batteries 6-9 were subjected toovercharging at 0.8 A (1C) from charged state at an environmentaltemperature of 20° C., and it was examined whether abnormal heatgeneration occurred or not in the batteries. The number of cells among20 cells in which abnormal heat generation occurred is shown in Tables 1and 2.

Furthermore, as high-temperature storage tests, the batteries in chargedstate were left to stand at 80° C. for 4 days, and the dischargecapacity at 1C was compared with the discharge capacity before storing,and capacity recovery rate after storing was calculated. (Capacityrecovery rate after storing=(1C discharge capacity after storing)/(1Cdischarge capacity before storing)×100(%)).

TABLE 1 (Example) Occurrence of abnormal heat Recovery rate after No.Additives generation storage (%) 1 o-Terphenyl (2%) + 0/20 75triphenylene (0.2%) 2 Cyclohexylbenzene (2%) + 0/20 85 biphenyl (0.2%) 3Cyclohexylbenzene (2%) + 2/20 82 o-terphenyl (0.2%) 4 Cyclohexylbenzene(2%) + 0/20 84 biphenyl (0.2%) + o-terphenyl (0.2%) 5 Cyclohexylbenzene(2%) + 0/20 83 biphenyl (0.2%) + o-terphenyl (0.2%) + triphenylene(0.1%)

TABLE 2 (Comparative Example) Occurrence of abnormal heat Recovery rateafter No. Additives generation storage (%) 6 No 20/20 87 7 Biphenyl (2%) 0/20 17 8 Cyclohexylbenzene (2%) 13/20 85 9 o-Terphenyl (2%)  7/20 6910 Biphenyl (0.2) 14/20 82

As shown in Table 2, in the battery 6 having no additives, thephenomenon of abnormal heat generation occurred in all of 20 cells whenthey were subjected to overcharging. Hitherto, the safety of batterieshas been ensured by providing a plurality of safety mechanismscomprising a protective circuit for charging voltage and a currentinterrupting mechanism, but the abnormal heat generation may occur incase no safety protection was provided as in the Comparative Example 1.

It can be seen that in the battery 7 of Comparative Example 2 in whichbiphenyl was added as the additive, abnormal heat generation did notoccur even when it was subjected to overcharging, and safety could beensured, but the recovery rate after storing at high temperatures wasvery low, namely, 17%.

This battery was disassembled after storing and analyzed to find a filmwhich was considered to be a polymerization product was formed on thesurface of the positive electrode, and it was presumed that the recoveryrate decreased due to the hindrance to charging and discharging reactionof lithium ion.

Furthermore, in the battery 8 of Comparative Example 3 in which onlycyclohexylbenzene high in reaction starting potential was contained, therecovery rate after storing at high temperatures was high, namely, 85%,and this battery showed characteristics substantially equal to those ofthe battery 6 containing no additives, but was insufficient in safety atthe time of overcharging and more than half of the cells resulted inabnormal heat generation.

In the case of addition of o-terphenyl which was relatively high inreaction starting potential, ignition rate at overcharging somewhatdecreased, but the decrease was still insufficient and, further, therecovery rate after storing was also insufficient.

When the amount of biphenyl of low reaction starting potential wasreduced, the recovery rate after storing increased, but safety atovercharging could not be ensured as in the battery 10 of ComparativeExample 5.

As explained above, it is not easy to ensure both the safety atovercharging and the high-temperature storage characteristics by using asingle additive.

In comparison with the batteries of the comparative examples, in thebatteries such as batteries 1-5 of the present invention in which two ormore additives were contained, by adding a small amount of an additiveof relatively lower reaction starting potential (biphenyl, o-terphenyl,triphenylene) in each system, the recovery rate after storing wasimproved and a recovery rate of more than 70% was maintained, and,moreover, since the additive of lower reaction starting potential whichslightly reacted during the overcharging increased the polarization atovercharging, the additive of higher reaction starting potential startedthe reaction at the early stage to enhance the safety at overcharging.Thus, batteries superior in recovery characteristics in storing and highin safety at overcharging could be realized.

From the point of maintaining the safety at overcharging, the amount ofcyclohexylbenzene is preferably not less than 1.0% by weight and notmore than 5.0% by weight.

Furthermore, from the point of maintaining the recovery characteristicsin storing, the amount of biphenyl or triphenylene is preferably notless than 0.01% by weight and less than 1.0% by weight.

INDUSTRIAL APPLICABILITY

As explained above, the present invention can provide batteries havinghigh safety against overcharging and excellent in recoverycharacteristics in storing at high temperatures by combining additivesto electrolytic solutions.

Portable telephones, portable information terminal devices, cam coders,personal computers, PDA, portable audio devices, electric cars, electricsources for road leveling, and the like which are high in safety can beprovided by using the non-aqueous type electrolyte secondary batteriesas mentioned above.

1. An electrolytic solution for non-aqueous type batteries having apositive electrode comprising a material containing a lithium-containingmetal oxide as a positive electrode active material and a negativeelectrode comprising a material containing graphite as a negativeelectrode active material, characterized in that the non-aqueouselectrolytic solution contains a non-aqueous solvent mainly composed ofa cyclic carbonate and a chain carbonate in which a lithium salt isdissolved as a solute, and further contains not less than 1.0% by weightand not more than 5.0% by weight of cyclohexylbenzene and not less than0.01% by weight and less than 1.0% by weight of biphenyl based on thetotal amount of the non-aqueous electrolytic solution are contained. 2.An electrolytic solution for non-aqueous type batteries according toclaim 1, which further comprises not less than 0.01% by weight and lessthan 1.0% by weight of o-terphenyl.
 3. An electrolytic solution fornon-aqueous type batteries according to claim 1, which further compriseso-terphenyl and triphenylene, and the total amount of o-terphenyl,triphenylene, cyclohexylbenzene and biphenyl is 0.4-5% by weight basedon the total amount of the non-aqueous electrolytic solution.
 4. Anelectrolytic solution for non-aqueous type batteries according to claim1, wherein the cyclic carbonate is at least one compound selected fromethylene carbonate (EC), propylene carbonate (PC), butylene carbonate(BC) and vinylene carbonate (VC).
 5. An electrolytic solution fornon-aqueous type batteries according to claim 1, wherein the chaincarbonate is at least one compound selected from dimethyl carbonate(DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC),methylpropyl carbonate (MPC) and ethylpropyl carbonate (EPC).
 6. Anon-aqueous type secondary battery having a positive electrodecomprising a material containing a lithium-containing metal oxide as apositive electrode active material, a negative electrode comprising amaterial containing graphite as a negative electrode active material anda non-aqueous electrolytic solution, characterized in that thenon-aqueous electrolytic solution contains a non-aqueous solvent mainlycomposed of a cyclic carbonate and a chain carbonate in which a lithiumsalt is dissolved as a solute, and further contains not less than 1.0%by weight and not more than 5.0% by weight of cyclohexylbenzene and notless than 0.01% by weight and less than 1.0% by weight of biphenyl basedon the total amount of the non-aqueous electrolytic solution arecontained.
 7. A non-aqueous type secondary battery according to claim 6,which further comprises not less than 0.01% by weight and less than 1.0%by weight of o-terphenyl.
 8. A non-aqueous type secondary batteryaccording to claim 6, which further comprises o-terphenyl andtriphenylene, and the total amount of o-terphenyl, triphenylene,cyclohexylbenzene and biphenyl is 0.4-5% by weight based on the totalamount of the non-aqueous electrolytic solution.
 9. A non-aqueous typesecondary battery according to claim 6, wherein the cyclic carbonate isat least one compound selected from ethylene carbonate (EC), propylenecarbonate (PC), butylene carbonate (BC) and vinylene carbonate (VC). 10.A non-aqueous type secondary battery according to claim 6, wherein thechain carbonate is at least one compound selected from dimethylcarbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC),methylpropyl carbonate (MPC) and ethylpropyl carbonate (EPC).
 11. Abattery comprising an electrolytic solution in which an electroylyte isdissolved in a non-aqueous solvent, the electrolytic solution comprisingtwo or more organic compounds added thereto, said two or more organiccompounds differing in oxidative polymerization potential, with aproviso that the ratio of the percent by weight of the organic compoundof relatively higher oxidative polymerization reaction potential and theorganic compound of relatively lower oxidative polymerization reactionpotential is not lower than 10:1 and not higher than 4:1, wherein theorganic compound of relatively higher oxidative polymerization reactionpotential is cyclohexylbenzene and the organic compound of relativelylower oxidative polymerization reaction potential is biphenyl, whereinthe battery is a secondary battery.